Construction Of Multifunctional Enzyme@MOF Catalysts For Asymmetric Sequential Reaction

With the development of global catalyst industry,the enzyme has attracted extensive attention in the field of organic synthesis as a biodegradable green biocatalyst.However,the development of photoenzyme reaction is still at the initial stage.Various active sites can be connected by metal organic framework(MOF)materials which are bridges from homogeneous to heterogeneous reactions.Multifunctional MOF-based catalysts have been attained great achievement and progress.However,there are few researches on the combination of selective site of enzyme with the active site of photocatalysis or other molecular catalysis sites in MOF materials to construct multifunctional catalysts.Therefore,the main works are as follows:1.To match the pore size of lipase,the mesoporous UiO-67 was constructed by post-synthetic modification and ligand removal strategy.The Ru-HP-UiO-67-GH photocatalyst was obtained by exchanging Ru-HP-UiO-67-GH onto HP-UiO-67-GH framework using post-synthetic ligand exchange strategy,and the mesoporous structure was retained.Finally,the lipase PPL was immobilized in Ru-HP-UiO-67-GH to obtain the enzyme@MOF composite material,PPL@Ru-HP-UiO-67-GH.A series of characterization and catalytic tests demonstrated that the multifunctional catalyst had been successfully prepared.The yield and ee value of asymmetric photoenzyme sequential reaction catalyzed by PPL@Ru-HP-UiO-67-GH were 27 % and 93 %,respectively.2.Pd/Ru-HP-UiO-67-GH with active sites of molecular catalysis and photocatalysis was constructed by using ligand exchange strategy,and then Pd/Ru-HPUiO-67-GH was used to immobilize lipase to obtain the multifunctional catalyst of Enzyme@MOF,PPL@Pd/Ru-HP-UiO-67-GH.A series of characterization and catalytic tests demonstrated that the multifunctional catalyst with excellent catalytic activity had been successfully prepared.C-H arylation-asymmetric photobiological sequential reaction was catalyzed by PPL@Pd/Ru-HP-UiO-67-GH.As a result,the yield of C-H aryl product was 79 % while the yield and ee value of photoenzyme sequential reaction were 24 % and 91 % respectively.